WO2014182018A1 - Catalyseur à oxydes mixtes mésoporeux, procédé pour le préparer et procédé de synthèse de 1,3-butadiène l'utilisant - Google Patents

Catalyseur à oxydes mixtes mésoporeux, procédé pour le préparer et procédé de synthèse de 1,3-butadiène l'utilisant Download PDF

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WO2014182018A1
WO2014182018A1 PCT/KR2014/003950 KR2014003950W WO2014182018A1 WO 2014182018 A1 WO2014182018 A1 WO 2014182018A1 KR 2014003950 W KR2014003950 W KR 2014003950W WO 2014182018 A1 WO2014182018 A1 WO 2014182018A1
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oxide catalyst
average pore
catalyst
mesoporous
solution
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PCT/KR2014/003950
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Korean (ko)
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서명지
고동현
차경용
강전한
김대철
남현석
최대흥
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(주) 엘지화학
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Priority to CN201480002027.2A priority Critical patent/CN104519995B/zh
Priority to JP2015521565A priority patent/JP5907637B2/ja
Priority to US14/418,027 priority patent/US9782765B2/en
Priority to EP14795346.7A priority patent/EP2862626B1/fr
Publication of WO2014182018A1 publication Critical patent/WO2014182018A1/fr

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    • C07C11/167—1, 3-Butadiene
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Definitions

  • the present invention relates to a mesoporous composite oxide catalyst, a method for preparing the same, and a method for synthesizing 1,3-butadiene using the same. Specifically, a specific pore silica is introduced into a multicomponent bismuth-molybdate catalyst to produce a complex oxide having a high surface area.
  • the present invention relates to a mesoporous complex oxide catalyst, a method for preparing the same, and a method for synthesizing 1,3-butadiene using the same, by providing a catalyst to improve butene conversion, 1,3-butadiene selectivity, yield, and economic feasibility.
  • 1,3-butadiene is one of the main raw materials of synthetic rubber, whose price fluctuates rapidly in connection with supply and demand in the petrochemical industry.
  • Methods of preparation include naphtha cracking, direct dehydration of normal-butenes, and oxidative dehydrogenation of normal-butenes.
  • the method of producing by naphtha cracking has the advantage that the price competitiveness is higher than other processes, but since naphtha cracking is not the only production process of butadiene, it is difficult to increase the production of butadiene only because it is linked with the supply and demand of ethylene and propylene.
  • the disadvantage is that the investment is made on a large scale.
  • Coprecipitation is generally used for the production of multicomponent metal oxide catalysts such as bismuth-molybdate catalysts.
  • the coprecipitation method is a method of preparing a catalyst by mixing and precipitating two or more metal solutions by adjusting the pH, and the process is simple, and industrially convenient to obtain high purity powder at low cost.
  • changes in pH and concentration occur, so that it is difficult to obtain a uniform fine particle powder.
  • a high firing temperature is required to form the crystal phase of the composite oxide catalyst, aggregation of particles occurs, which has a disadvantage of reducing the surface area of the catalyst acting as a mechanism of adsorption-reaction-desorption at the surface. It is known that the surface area of the composite oxide catalysts composed of only metal oxides prepared by the coprecipitation method is generally about 10 m 2 / g.
  • EP 2343123 discloses a technique of dispersing silica particles such as fumed silica using multicomponent bismuth-molybdate containing at least cobalt or nickel.
  • the present invention has a high surface area by the introduction of specific porosity silica, so that conversion of butene, selectivity and yield of 1,3-butadiene for oxidative dehydrogenation of normal-butene We want to provide technology with economical efficiency while improving the quality.
  • an object of the present invention is to prepare a novel mesoporous composite oxide catalyst having a high surface area by adding silica having a specific pore structure as a composite oxide catalyst for synthesizing 1,3-butadiene, and a preparation method thereof.
  • Another object of the present invention is to efficiently synthesize 1,3-butadiene while improving the conversion of butene, selectivity and yield of 1,3-butadiene to oxidative dehydrogenation of normal-butene using the catalyst. To provide a way.
  • E is one or more selected from Group 1 elements of the periodic table, a is 0.001 to 13 , b, c, d and e are respectively 0.001 to 10, x is an integer from 1 to 99, y is different Is a value determined by the component to match the valence),
  • It has pores and the average pore volume of the pores is characterized in that 0.01 to 2cm 3 / g and the average pore size is 2 to 50nm.
  • the precursor mixture solution was added to the precursor solution of Mo and coprecipitated. Then, in 1 to 99% by weight of the solution of the coprecipitation, the average pore volume of the pores was 0.5-2 cm 3 / g, the average pore size was 2-10 nm, and the surface area was 500. 99 to 1% by weight of silica powder of -1400 m 2 / g Drying to obtain a solid powder; And
  • the solid powder of the third step is formed and calcined to obtain a mesoporous complex oxide catalyst represented by the following Chemical Formula 1, having pores, having an average pore volume of 0.01 to 2 cm 3 / g and an average pore size of 2 to 50 nm. It comprises; a.
  • E is one or more selected from Group 1 elements of the periodic table, a is 0.001 to 13 , b, c, d and e are respectively 0.001 to 10, x is an integer from 1 to 99, y is different Is a value determined by the component to match the valence)
  • a mesoporous complex oxide catalyst represented by the following Chemical Formula 1, having pores, having an average pore volume of 0.01 to 2 cm 3 / g and an average pore size of 2 to 50 nm. It comprises; a.
  • E is one or more selected from Group 1 elements of the periodic table, a is 0.001 to 13 , b, c, d and e are respectively 0.001 to 10, x is an integer from 1 to 99, y is different Is a value determined by the component to match the valence)
  • the method for synthesizing 1,3-butadiene of the present invention is characterized by oxidative dehydrogenation of normal-butene using the mesoporous composite metal oxide catalyst described above as a catalyst.
  • a specific porous silica is introduced into a multicomponent bismuth-molybdate catalyst to provide a complex oxide catalyst for synthesizing 1,3-butadiene having a high surface area, thereby converting butene into It improves the selectivity and yield of 1,3-butadiene and reduces the amount of metal used than before, thereby reducing the cost of catalyst production.
  • FIG. 1 is a flowchart of synthesizing a composite oxide catalyst including silica having a crystal structure of MCM-41 type according to a first embodiment of the present invention.
  • FIG. 2 is a flowchart of synthesizing a composite oxide catalyst including silica having a SBA-15 type crystal structure according to a second embodiment of the present invention.
  • FIG. 3 is a flowchart for synthesizing a metal oxide catalyst prepared by the co-precipitation method according to the prior art.
  • FIG. 4 is an X-ray diffraction spectrum of a metal oxide catalyst prepared according to the flowchart of FIG. 3 and a composite oxide catalyst containing 40 wt% of silica prepared according to the flowchart of FIG. 2 and having a SBA-15 type crystal structure. .
  • FIG. 5 is a small angle XRD spectrum of silica having a crystal structure of MCM-41 type prepared according to the flowchart of FIG. 1.
  • FIG. 6 is a small angle XRD spectrum of silica having a SBA-15 type crystal structure prepared according to the flowchart of FIG. 2.
  • the present invention has a technical feature to provide a mesoporous composite oxide catalyst as a catalyst for synthesizing 1,3-butadiene.
  • 'mesoporous complex oxide catalyst' used in the present invention refers to a structure in which the complex oxide catalyst is sufficiently introduced into the pores of the carrier in addition to the surface of the silica carrier unless otherwise stated.
  • the catalyst is represented by the formula
  • E is one or more selected from Group 1 elements of the periodic table
  • a is 0.001 to 13
  • b, c, d and e are respectively 0.001 to 10
  • x is an integer from 1 to 99
  • y is different It is a value determined in order to match the valence by the components), characterized in that the pores have an average pore volume of 0.01 to 2cm 3 / g and an average pore size of 2 to 50nm.
  • the catalyst is characterized in that it has a high surface area of 20 to 1400m 2 / g.
  • the average pore volume of the pores in the catalyst may be 0.01 to 1.5cm 3 / g and the average pore size is 2 to 10nm, the catalyst may have a high surface area of 50 to 900m 2 / g.
  • the average pore volume of the pores in the catalyst may be 0.03 to 1 cm 3 / g and the average pore size is 2 to 5 nm, the catalyst may have a high surface area of 83 to 879 m 2 / g.
  • E may be at least one of cesium (Cs) and rubidium (Rb).
  • a may be 1 to 12, or 8 to 12.
  • b, c, d and e may be 1 to 10, or 1 to 9, respectively.
  • x may be an integer from 1 to 90, or an integer from 30 to 60.
  • the SiO 2 is one example, an average pore volume of pores 0.5-2 cm 3 / g, or from 1.1 to 1.4cm 3 / g and the average pore size of 2-10nm, or from 3 to 5nm and a specific surface area 500-1400m 2 / g Or 880 to 1337 m 2 / g.
  • the SiO 2 may have a crystal structure of MCM-41 type and show the spectrum of FIG. 5.
  • the silica having a crystal structure of the MCM-41 type may have peaks in the 2 theta ranges of 1.50 to 2.38, 3.40 to 3.89, and 4.12 to 4.41 in a small angle X-ray diffraction analysis (small angle XRD). (FIG. 5).
  • the SiO 2 may have a SBA-15 type crystal structure and show the spectrum of FIG. 6.
  • the SBA-15 type silica having a crystal structure may have peaks in the range of 0.60 to 1.18, 1.49 to 1.73, and 1.80 to 1.98 in small angle X-ray diffraction analysis (small angle XRD). (FIG. 6).
  • the mesoporous composite metal oxide catalyst according to the present invention may be prepared, for example, in the following manner:
  • the precursor mixture solution was added to the precursor solution of Mo and coprecipitated. Then, in 1 to 99% by weight of the solution of the coprecipitation, the average pore volume of pores was 0.5-2 cm 3 / g, the average pore size was 2-10 nm, and the surface area was 99-1 wt% of silica powder with 500-1400m 2 / g Drying to obtain a solid powder; And
  • the solid powder of the third step is formed and calcined to obtain a mesoporous complex oxide catalyst represented by the following Chemical Formula 1, having pores, having an average pore volume of 0.01 to 2 cm 3 / g and an average pore size of 2 to 50 nm. It comprises; a.
  • E is one or more selected from Group 1 elements of the periodic table, a is 0.001 to 13 , b, c, d and e are respectively 0.001 to 10, x is an integer from 1 to 99, y is different Is a value determined by the component to match the valence)
  • the mesoporous composite metal oxide catalyst according to the present invention may be prepared in the following manner:
  • the average pore volume of the pores is 0.5-2 cm 3 / g, the average pore size is 2-10nm and the surface area is 500-1400m 2 / g Blend 99 to 1% by weight of silica powder Obtaining a solid powder;
  • a mesoporous complex oxide catalyst represented by Chemical Formula 1 having pores, having an average pore volume of 0.01 to 2 cm 3 / g and an average pore size of 2 to 50 nm. It comprises; a.
  • the silica powder may be prepared by adding a silica source to a basic aqueous solution in which a cationic surfactant is dispersed or an acidic aqueous solution in which a block copolymer is dispersed, followed by heat or pressure treatment. .
  • Silica obtained by drying and calcining the heat or pressure-treated solution may be added to the metal precursor solution, dried and calcined to obtain a mesoporous complex oxide catalyst.
  • the average pore size of mesoporous silica can be increased to 2 ⁇ 50nm or more by adding a heat treatment temperature, heat treatment time and an expansion agent such as trimethyl benzene (TMB).
  • TMB trimethyl benzene
  • the composite metal oxide catalyst of the present invention may be obtained by mixing a metal oxide and mesoporous silica obtained by the coprecipitation method and calcining.
  • the silica powder may be a cationic surfactant solution and a stirred solution of a silica source after heat treatment under the conditions of 333 to 373K, pH-controlled, dried and calcined to have a crystal structure of MCM-41 type.
  • the cationic surfactant solution may be, for example, at least one selected from cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride. have.
  • the silica source may be of a kind having a reactor condensable with the surfactant, for example, may be one or more selected from tetramethylorthosilicate, tetraethylorthosilicate and sodium silicate.
  • the silica powder may be one having a SBA-type crystal structure by heat-treating the calcined solution of the block copolymer solution and the silica source after heat treatment under the conditions of 333K to 373K.
  • the block copolymer may be a block copolymer including an ethylene glycol block and a propylene glycol block, and for example, a diblock copolymer of an ethylene glycol block and a propylene glycol block, and an ethylene glycol block, a propylene glycol block, and an ethylene glycol block. It may be at least one selected from triblock copolymer comprising a.
  • the silica source may be selected from the above-mentioned kind.
  • Drying in the present invention can be carried out under 323 to 473K.
  • the firing in the present invention can be carried out under 673-873K, for example.
  • the heat or pressure-treated silica mixture solution is not limited to use through the drying and firing step.
  • nitrate or ammonium salt may be used as the metal precursor solution.
  • cesium when cesium is selected as the E component in Chemical Formula 1, cesium, cobalt, iron, and bismuth precursors are simultaneously dissolved in distilled water and molybdenum precursors are separately dissolved in distilled water, followed by mixing. Acidic solutions (eg, nitric acid) and the like can be added. When the precursors are completely dissolved, the precursor solution containing cesium, cobalt, iron and bismuth is injected into the precursor solution containing molybdenum to co-precipitate the metal components. The co-precipitated solution is stirred for 0.5 to 24 hours, preferably 1 to 2 hours, to allow sufficient coprecipitation.
  • Acidic solutions eg, nitric acid
  • Mesoporous silica is added to the stirred solution and dried at 323 to 473K for 12 to 24 hours to remove moisture and other liquid components to obtain a solid sample.
  • the solid sample thus formed may be formed into a hollow, pellet, or spherical shape and placed in an electric furnace, followed by heat treatment at a temperature of 673 to 873 K to prepare a composite oxide catalyst.
  • mesoporous silica may be mixed with the dried sample of the stirred solution to form a complex oxide catalyst.
  • the catalyst is not limited thereto, but may be applied to an oxidative dehydrogenation reaction of normal-butene.
  • 1,3-butadiene can be synthesized by oxidative dehydrogenation of normal-butene using the catalyst described above.
  • the reactant normal-butene is adsorbed to the catalyst, and then oxygen in the catalyst lattice is reacted with two hydrogens of the adsorbed butene to produce 1,3-butadiene and water, and the reactant molecular oxygen is the catalyst lattice.
  • the reaction proceeds by filling the empty oxygen sites of.
  • the catalyst was used in a reactant contained in a molar ratio of 1: 0.5 to 2: 2 to 20 to 5 to 20.
  • reaction temperature 250 to 350 °C and space velocity based on butenes of 50 to 5000 h -1.
  • reaction temperature and space velocity may be in a space velocity range based on a reaction temperature of 280 to 330 ° C. and butene of 50 to 1000 h ⁇ 1.
  • the oxidative dehydrogenation reaction may be carried out while filling the catalyst into a fixed bed in a shell-tube reactor having a fixed multiple tube and having a fruit circulation on the outside, and reactants continuously pass through the catalyst bed.
  • the catalyst 1000 to 2,000cc may be performed using a shell-tube reactor including a multi-tube fixed and filled with a fruit circulation on the outside.
  • the method for synthesizing 1,3-butadiene according to the present invention comprises charging a hydroxide catalyst prepared according to the above-mentioned preparation method into a fixed bed; An oxidative dehydrogenation reaction was conducted while continuously passing a reactant containing a C4 mixture including butene, oxygen, nitrogen, and steam through the catalyst bed of the reactor to obtain a dehydrogenation product mixture, and then, from the dehydrogenation product mixture, 1, It may include a purification process for separating 3-butadiene, or may include the step of recycling to the reactant if necessary.
  • the obtained 1,3-butadiene may comprise a purification process consisting of quenching, compression, absorption, degassing and butadiene separation process.
  • the product exiting the reactor through the quenching process is water and heavy components are removed and delivered to the absorption process through the compression process at a pressure suitable for the absorption process.
  • the absorption process absorbs 1,3-butadiene using solvent to separate nitrogen, oxygen and COx, and the degassing process removes gas and by-products absorbed together with the solvent. Finally, 1,3-butadiene and solvent may be separated using physical property differences through the butadiene separation process. If necessary, the method may further include a step of circulating the starting material for each process.
  • the surfactant cetyltriethylammonium bromide (CTABr) was dissolved in distilled water at 60 ° C., and the sodium silicate solution was prepared so that the final stoichiometric ratio was 0.12 Na 2 O: 0.5 SiO 2: 0.1 CTABr: 30 H 2 O. The mixture was stirred at 60 ° C. for 1 hour to prepare an emulsion solution.
  • the emulsion solution was heat-treated at 100 ° C. for 48 hours, and titrated with an aqueous nitric acid solution or an aqueous hydrochloric acid solution to maintain a pH of 10 as the synthesis process proceeded to prepare a silica-mixed solution with silica.
  • the silica mixed solution was filtered, washed with distilled water or ethanol and dried at 100 ° C. to obtain a solid sample.
  • the solid sample was placed in an electric furnace and calcined at 550 ° C. for 5 hours to add silica to a metal precursor solution using Cs as E in Chemical Formula 1 to prepare a composite oxide catalyst.
  • metal precursors include cobalt nitrate (Co (NO3) 2.6H2O), iron nitrate (Fe (NO3) 3.9H2O), bismuth nitrate (Bi (NO3) 2.5H2O), cesium nitrate (CsNO3) and ammonium Molybdate ((NH 4) 6 Mo 7 O 2 4.4H 2 O) was used.
  • bismuth nitrate, cesium nitrate, cobalt nitrate and iron nitrate were dissolved and stirred in an aqueous nitric acid solution to prepare a metal nitrate aqueous solution.
  • ammonium molybdate was dissolved in distilled water in a double jacket reactor while maintaining a constant temperature of 40 °C, the metal nitrate aqueous solution was added to the coprecipitated and stirred for 1 hour at 40 °C.
  • the stirred solution was dried and ground in an oven at 120 ° C. for 18 hours, and then the mesoporous silica was added to obtain a solid powder.
  • the solid powder was kneaded with distilled water and alcohol and extruded into a pellet shape having a diameter of 6 mm and a length of 6 mm, and the molded body was heat treated at 450 ° C. for 7 hours to form a mesoporous composite metal having a composition of 30 wt% Mo 12 Bi 1 Fe 2 Co 5 Cs 0.10 y + 70 wt% SiO 2.
  • An oxide catalyst and a mesoporous composite metal oxide catalyst having a composition of 60 wt% Mo 12 Bi 1 Fe 2 Co 5 Cs 0.10 y + 40 wt% SiO 2 were prepared, respectively.
  • the preparation of the catalyst is shown in FIG. 1.
  • a triblock copolymer manufactured by BASF
  • poly (ethylene glycol) -poly (propylene glycol) -poly (ethylene glycol) is dissolved in an aqueous hydrochloric acid solution at 40 ° C.
  • TEOS Tetraethylortho silicate
  • the emulsion solution was heat-treated at 40 ° C. for 24 hours and at 100 ° C. for 12 hours to prepare a silica mixed solution.
  • the silica mixed solution was filtered, washed with distilled water or ethanol and dried at 100 ° C. to obtain a solid sample.
  • Mesoporous silica prepared by placing the solid sample in an electric furnace and calcining at 550 ° C. for 5 hours was added to a metal precursor solution using Cs as E in Chemical Formula 1 to prepare a composite oxide catalyst.
  • metal precursors include cobalt nitrate (Co (NO3) 2.6H2O), iron nitrate (Fe (NO3) 3.9H2O), bismuth nitrate (Bi (NO3) 2.5H2O), cesium nitrate (CsNO3) and ammonium Molybdate ((NH 4) 6 Mo 7 O 2 4.4H 2 O) was used.
  • bismuth nitrate, cesium nitrate, cobalt nitrate and iron nitrate were dissolved and stirred in an aqueous nitric acid solution to prepare an aqueous metal nitrate solution.
  • ammonium molybdate was dissolved in distilled water in a double jacket reactor while maintaining a constant temperature of 40 °C, the metal nitrate aqueous solution was added to the coprecipitated and stirred for 1 hour at 40 °C.
  • the stirred solution was dried and ground in an oven at 120 ° C. for 18 hours, and then the mesoporous silica was added to obtain a solid powder.
  • the solid powder was kneaded with distilled water and alcohol and extruded into a pellet shape having a diameter of 6 mm and a length of 6 mm, and the molded body was heat-treated at 450 ° C. for 7 hours to form a mesoporous composite metal having a composition of 30 wt% Mo 12 Bi 1 Fe 2 Co 5 Cs 0.10 y + 70 wt% SiO 2.
  • a mesoporous composite metal oxide catalyst having a composition of an oxide catalyst and 60 wt% Mo 12 Bi 1 Fe 2 Co 5 Cs 0.10 y + 40 wt% SiO 2 was prepared, respectively.
  • the preparation of the catalyst is shown in FIG. 2.
  • Cobalt nitrate Co (NO3) 2.6H2O
  • iron nitrate Fe (NO3) 3.9H2O
  • bismuth nitrate Bi (NO3) 2.5H2O
  • Cesium nitrate CsNO 3
  • ammonium molybdate ((NH 4) 6 Mo 7 O 2 4.4H 2 O) were used and prepared in the following manner.
  • bismuth nitrate, cesium nitrate, cobalt nitrate and iron nitrate were dissolved and stirred in an aqueous nitric acid solution to prepare an aqueous metal nitrate solution.
  • ammonium molybdate was dissolved in distilled water in a double jacket reactor while maintaining a constant temperature of 40 °C, the metal nitrate aqueous solution was added to the coprecipitated and stirred for 1 hour at 40 °C.
  • the stirred solution was dried in an oven at 120 ° C. for 18 hours, and the pulverized powder was kneaded with distilled water and alcohol to be extruded into pellets having a diameter of 6 mm and a length of 6 mm. Catalyst was prepared. The preparation of the catalyst is shown in FIG. 3.
  • Example 1-2 and Comparative Example 1 confirmed successful preparation through X-ray diffraction analysis and elemental component analysis (ICP-AES), X-ray diffraction analysis showed that the catalyst was CoMoO 4, (Co0 .7Fe0.3) MoO4, Bi2Mo3O12 was formed as a mixed phase, the element composition ratio of the catalyst prepared by elemental component analysis (ICP-AES) is Mo: Bi: Fe: Co: Cs of Bi It was confirmed that it was 12: 1: 2: 5: 0.1 when calculated by the relative ratio.
  • ICP-AES elemental component analysis
  • the results of X-ray diffraction analysis of the catalyst of Comparative Example 1 were 9.84 to 9.96, 13.02 to 13.20, 18.62 to 18.70, 23.18 to 23.26, 25.54 to 25.62, and 26.38 to 26.46. , The same as the 2 theta peak range of 28.30 to 28.38, 32.00 to 32.08, 33.58 to 33.66, and 45.04 to 45.12, confirming that the same catalyst crystal phase as that of Comparative Example 1 was successfully formed for Example 2 prepared according to the present invention. Can be.
  • the MCM-41 ranges from 2 to 50 nm as defined by the IUPAC. Cylindrical mesopores have a well-aligned structure in three dimensions and the spectrum of FIG. Corresponds to the characteristic peak. Silica having a crystal structure of MCM-41 type prepared according to the flow chart of FIG. 1 has peaks at 2 theta ranges of 1.50 to 2.38, 3.40 to 3.89, and 4.12 to 4.41 in small angle XRD. (FIG. 5).
  • the pore silica of the MCM-41 type is calculated by BET formula, t-plot, and BJH method through the adsorption isotherm of nitrogen, respectively.
  • the surface area is 1337m 2 / g
  • the average pore volume is 1.4cm 3 / g
  • the average pore size is 3.0 nm.
  • the metal oxide catalyst has a surface area, an average pore volume, and an average pore size as shown in Table 1 below.
  • SBA - 15 is according to the definition of IUPAC Cylindrical mesopores ranging from 2 to 50 nm are well aligned in three dimensions
  • the spectrum of FIG. 6 is the characteristic peak for this structure.
  • Silica having a crystal structure of SBA-15 type prepared according to the flow chart of FIG. 2 has a peak at 2 theta ranges of 0.60 to 1.18, 1.49 to 1.73, and 1.80 to 1.98 in small angle XRD. (FIG. 6).
  • a mesoporous composite metal oxide catalyst having a composition of 30 wt% Mo 12 Bi 1 Fe 2 Co 5 Cs 0.10 y + 70 wt% SiO 2 and a mesoporous composite having a composition of 60 wt% Mo 12 Bi 1 Fe 2 Co 5 Cs 0.10 y + 40 wt% SiO 2 prepared by adding porous silica having the above characteristics in Example 2
  • the metal oxide catalyst exhibited surface area, average pore volume and average pore size as shown in Table 2 below.
  • the surface area is 3.3m 2 / g
  • the average pore volume 0.01cm 3 / g
  • the average pore size was 39nm.
  • Normal-butene was supplied together with oxygen, nitrogen, and steam in the reactor, wherein the molar ratio of butene: oxygen: nitrogen: steam was set to 1: 0.5: 8: 5, and the space velocity (GHSV) was based on normal-butene. 250h-1,
  • the butene flow rate was controlled using a mass flow controller (MFC) for liquids, oxygen and nitrogen were supplied using a mass flow controller for gas, and the steam flow was injected using a liquid pump. Steam was injected into the vaporizer in the form of water, vaporized at 200 ° C., mixed with other reactants, butenes, oxygen, and nitrogen, and introduced into the reactor.
  • MFC mass flow controller
  • the catalyst was pretreated with an air atmosphere at 400 ° C. for 2 hours before the reaction was introduced, and the reaction product was continuously introduced into the catalyst bed while maintaining the reaction temperature at 320 ° C., and the product was analyzed by gas chromatography at 1-2 hour intervals.
  • the product stream included carbon dioxide, carbon monoxide, C4 by-products, normal-butene, trans-2-butene, cis-2-butene, oxygen, nitrogen and the like, in addition to the targeted 1,3-butadiene.
  • % Conversion number of moles of normal-butene reacted / number of moles of normal-butene fed x 100
  • At least 40 wt% or more of the composite oxide catalyst for synthesizing 1,3-butadiene may be replaced with a specific porous silica, such that a certain amount or more may be replaced with the specific porous silica. Because of this, it has an economical efficiency to reduce the catalyst production cost by reducing the metal consumption than conventional.
  • the mesoporous composite metal oxide catalyst for synthesis of high surface area 1,3-butadiene having improved catalytic performance and economical efficiency by introducing specific porous silica in the preparation of 1,3-butadiene synthesis catalyst. It was confirmed that it can provide.

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Abstract

La présente invention concerne un catalyseur à oxydes mixtes mésoporeux, un procédé pour le préparer et un procédé pour effectuer la synthèse du 1,3-butadiène au moyen dudit catalyseur. Selon la présente invention, la silice mésoporeuse est ajoutée lorsqu'un catalyseur utilisé pour effectuer la synthèse du 1,3-butadiène est préparé, ce qui améliore la surface catalytique active et, par voie de conséquence, le taux de conversion du n-butène, la sélectivité du 1,3-butadiène et son rendement, tout en réduisant la quantité de métal, et de ce fait, la présente invention permet également de parvenir à une efficacité d'ordre économique en ce sens où elle permet d'abaisser le coût de production de catalyseur.
PCT/KR2014/003950 2013-05-06 2014-05-02 Catalyseur à oxydes mixtes mésoporeux, procédé pour le préparer et procédé de synthèse de 1,3-butadiène l'utilisant WO2014182018A1 (fr)

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US14/418,027 US9782765B2 (en) 2013-05-06 2014-05-02 Mesoporous composite oxide catalyst, method for preparing the same and method for synthesizing 1,3-butadiene using the same
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JP2015527192A (ja) 2015-09-17
EP2862626B1 (fr) 2024-03-27
KR101796821B1 (ko) 2017-11-13
EP2862626A4 (fr) 2016-05-04
CN104519995A (zh) 2015-04-15
US20150151292A1 (en) 2015-06-04
US9782765B2 (en) 2017-10-10
KR101507686B1 (ko) 2015-03-31
KR20150024373A (ko) 2015-03-06
KR20140131872A (ko) 2014-11-14
JP5907637B2 (ja) 2016-04-26
EP2862626A1 (fr) 2015-04-22
CN104519995B (zh) 2016-11-23

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